Article comprising a fine-Grained metallic material and a polymeric material

ABSTRACT

Lightweight articles comprising a polymeric material at least partially coated with a fine-grained metallic material are disclosed. The fine-grained metallic material has an average grain size of 2 nm to 5,000 nm, a thickness between 25 micron and 5 cm, and a hardness between 200 VHN and 3,000 VHN. The lightweight articles are strong and ductile and exhibit high coefficients of restitution and a high stiffness and are particularly suitable for a variety of applications including aerospace and automotive parts, sporting goods, and the like.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of U.S. application Ser. No. 11/013,456,filed Dec. 17, 2004.

FIELD OF THE INVENTION

This invention relates to applying thick (>25 μm), fine-grained (averagegrain size 2 nm to 5,000 nm) metals, metal alloys or metal matrixcomposites with high specific strength, toughness and resilience (>0.25MPa) to polymeric substrates in order to achieve a structural shell.Articles made according to the invention find use in a variety ofapplications where the use of the high strength structural shell on apolymer or composite substrate allows for substantial weight savings.Applications include automotive components, aerospace parts, defenseparts, consumer products, medical components and sporting goods.Suitable industrial parts include, among others, tubes or shafts used,e.g., in sporting goods such as ski and hiking poles, fishing rods, golfclub shafts, hockey sticks, lacrosse sticks, baseball/softball bats,bicycle frames, skate blades, snow boards; plates such as golf club headface plates; as well as complex shapes such as sports racquets (tennis,racquetball, squash and the like), golf club heads, automotivegrill-guards; brake, gas or clutch pedals; fuel rails; running boards;spoilers; muffler tips, wheels, vehicle frames, structural brackets andthe like. Parts are at least partially coated with said fine-grainedmetallic materials.

The invention also relates to depositing fine-grained metallic materialsdirectly onto suitable substrates such as cylindrical, conical ortapered shafts. Alternatively, fine-grained metallic plates or foils andthe like can be formed and subsequently applied using adhesives tosuitable substrates to produce strong, ductile, lightweight componentsrequiring a high modulus of resilience, a high coefficient ofrestitution and a high torsional stiffness.

BACKGROUND OF THE INVENTION

A variety of applications require articles to be strong, wear resistant,lightweight and to display high specific strength, high impact toughnessand high flexural stiffness while being manufactured by a convenient andcost-effective method.

(2: Metal Coating Processes)

A number of metal deposition techniques including electrolytic,electroless plating and powder-coating processes are known to applymetallic coatings to surfaces of various articles such as sportinggoods, automotive articles and the like.

(2.1. Electroless Coating)

Electroless coating processes are used commercially particularly for Ni,Cu and Ag. Electroless coating deposition rates are low, typicallymil/hr (6.35 μm/hr) to 0.5 mil/hr (12.7 μm/hr) and yield an amorphousmicrostructure. Typical coating thickness values for electroless platingprocesses are much lower than 1 mil (25 μm) and primarily applied toenhance the appearance, or improve the scratch and the corrosionresistance. Leibowitz in U.S. Pat. No. 3,597,266 (1971) describes apopular electroless Ni plating process.

(2.2. Conventional Electroplating)

A variety of electroplating processes are known to deposit conventionalcoarse-grained metallic coatings on substrates at deposition rates thattypically exceed 1 mil/hr (25 μm/hr) and are commercially available fora number of chemistries including Cu, Co, Ni, Cr, Sn, Zn. In the case ofgalvanic coatings it is well known that after the coating has been builtup to a thickness of about 5-10 μm, it tends to become highly texturedand grows in a fashion whereby anisotropic and elongated columnar grainsprevail with typical grain widths of a few microns and grain lengths oftens of microns. Prior art thin coatings applied by conventionalelectroplating processes exhibit conventional average grain sizes (≧10μm) and do not significantly enhance the overall mechanical propertiesof the coated article, thus not providing a structural shell.

Donavan in U.S. Pat. No. 6,468,672 (2002) discloses a process forforming a decorative chromium plating having good corrosion resistanceand thermal cycling characteristics on a plastic substrate by firstdepositing an electrically conductive coating on the plastic substratefollowed by electrodepositing a high leveling semi-bright nickelelectroplate layer, followed by electrodepositing a bright nickelelectroplate layer, and finally followed by electrodepositing a chromiumlayer.

(2.3: Fine-Grained Electroplating)

Recently it has been recognized that a substantial reduction of theaverage grain size strongly enhances selected physical, chemical andmechanical properties of metallic materials. For example, in the case ofnickel, the ultimate tensile strength increases from 400 MPa (forconventional grain-sizes greater than 5 μm) to 1,000 MPa (grain size of100 nm) and ultimately to over 2,000 MPa (grain size 10 nm). Similarly,the hardness for nickel increases from 140 VHN (for conventionalgrain-sizes greater than 5 μm) to 300 VHN (grain size of 100 nm) andultimately to 650 VHN (grain size 10 nm). Electroplated fine-grainedmetallic materials of improved durability and performancecharacteristics are known in the prior art including:

Erb in U.S. Pat. No. 5,352,266 (1994), and U.S. Pat. No. 5,433,797(1995), assigned to the applicant of this application, describes aprocess for producing nanocrystalline metallic materials, particularlynanocrystalline nickel with an average grain size of less than 100 nmusing pulse electrodeposition and an aqueous electrolytic cell. Productsof the invention include wear resistant coatings and magnetic materials.

Palumbo DE 10,288,323 (2005) (=WO2004/001100 A1 2002) also assigned tothe applicant of this application, discloses a process for formingcoatings or freestanding deposits of nanocrystalline metals, metalalloys or metal matrix composites. The process employs tank, drum orselective plating processes. Novel nanocrystalline metal matrixcomposites and micro-components are disclosed as well.

(2.4: Alternative Fine-Grained Coating Processes)

Various patents disclose low temperature powder spray processes for thepreparation of metallic coatings.

Alkhimov in U.S. Pat. No. 5,302,414 (1991) describes a cold gas-dynamicspraying method for applying a coating to an article by introducingmetal or metal alloy powders, polymer powders or mechanical mixturesthereof into a gas stream. The gas and particles (average particle sizerange: 1 to 50 microns) form a supersonic jet (velocity: 300 to 1,200m/sec) at a temperature considerably below the fusing temperature of thepowder material. The jet is directed against an article of a metal,alloy or dielectric, thereby coating the article with the particles.

Tapphorn in U.S. Pat. No. 6,915,964 (2005) describes a spraying processfor forming coatings by solid-state deposition and consolidation ofpowder particles. The subsonic or sonic gas jet containing the particlesis directed onto the surface of an object. Due to the high velocityimpact and thermal plastic deformation, the powder particles adhesivelybond to the substrate and cohesively bond together to form consolidatedmaterials with metallurgical bonds. The powder particles and optionallythe surface of the object are heated to a temperature that reduces yieldstrength and permits plastic deformation at low flow stress levelsduring high velocity impact. No melting of the powder particles takesplace.

(3: Polymeric Substrates)

Suitable permanent substrates include polymer materials, whichoptionally can be filled with or reinforced with, e.g., metals and metalalloys, glass, ceramics, and carbon based materials selected from thegroup of graphite, graphite fibers and carbon nanotubes. For strengthand cost reasons, filled polymers are very desirable plastic substratematerials. The term “filled” as used herein refers to polymer resinswhich contain powdered (i.e., 0.2-20 microns) mineral fillers such astalc, calcium silicate, silica, calcium carbonate, alumina, titaniumoxide, ferrite, and mixed silicates which are commercially availablefrom a variety of sources having a filler content of up to about fortypercent by weight. If required, e.g., in the case of electricallynon-conductive or poorly conductive substrates and the use ofelectroplating for the coating deposition, the surface of the polymericsubstrates can be metallized to render it sufficiently conductive forplating. In this case the fine-grained coating layer is alwayssubstantially thicker than the metallized layer.

Poppe in U.S. Pat. No. 3,655,433 (1972) describes nonconductive plasticsubstrates particularly suitable for electroplating, whereby theadhesion of the metal to the plastic material is enhanced byincorporating between 1 and 25 percent by weight of a metal resinate inthe polymer. Crystalline polyolefins, such as polyethylene,polypropylene and propylene-ethylene copolymer, are modified withcalcium resinate, zinc resinate, aluminum resinate, sodium resinate,potassium resinate or ammonium resinate to improve the adhesion of metalthereto.

Ding in U.S. Pat. No. 6,509,107 (2003) discloses polyolefin compositionsthat are well suited to metal plating and are easily processed intoarticles by various molding methods. The blends of the inventionpreferably include polyolefin homopolymers or copolymers,acrylonitrile-butadiene-styrene polymers, and a blend of at least onestyrene monoolefin copolymer and at least one styrene diolefincopolymer. These blends have excellent platability and superior physicalproperties including enhanced rigidity, toughness, and dimensionalstability.

(4: Metallizing Polymeric Substrates)

Nowadays plastic materials are frequently used for decorative parts inautomotive and other applications due to their low cost and ease ofprocessing/shaping by various means. It is well known in the art thatplastic materials can be electroplated to achieve a particular aestheticfinish. Decorative chromium plating comprising successiveelectrodeposited layers of copper, nickel and chromium is the process ofchoice. The electrodeposit must adhere well to the underlying plasticsubstrate even in corrosive environments and when subjected to thermalcycling, such as are encountered in outdoor service. The prior artdescribes numerous processes for metallizing plastics to render themsuitable for electroplating by conditioning the substrate's surface toinsure electrodeposits adequately bond thereto resulting in durable andadherent metal deposits.

Liu in U.S. Pat. No. 4,604,168 (1986) describes a method of preparingthe surface of molded mineral-filled Nylon® to receive an adherentelectrodeposited metal coating comprising the steps of: exposing thesurface to a plasma glow discharge; vacuum depositing a film of chromiumor titanium onto the plasma-treated surface; vacuum depositing a nickelfilm onto the chromium or titanium film to prevent oxidation thereof;and then vacuum depositing a copper film onto the nickel film.

Stevenson in U.S. Pat. No. 4,552,626 (1985) describes a process formetal plating filled thermoplastic resins such as Nylon-6®. The filledresin surface to be plated is cleaned and rendered hydrophillic andpreferably deglazed by a suitable solvent or acid. At least a portion ofthe filler in the surface is removed, preferably by a suitable acid.Thereafter an electroless plating is applied to provide an electricallyconductive metal deposit followed by applying at least one metalliclayer by electroplating to provide a desired wear resistant and/ordecorative metallic surface.

Conrod in U.S. Pat. No. 5,376,248 (1994) describes a directmetallization process wherein plastic substrates may be electrolyticallyplated without the need for any prior electroless plating. The processuses a specially formulated post-activator composition at an elevatedtemperature to treat the activated substrate with an alkaline solutioncontaining an effective amount of metal ions such as Cu⁺2 which undergoa disproportionation reaction.

Joshi in U.S. Pat. No. 6,645,557 (2003) describes a method for forming aconductive metal layer on a non-conductive surface by contacting thenon-conductive surface with an aqueous solution or mixture containing astannous salt to form a sensitized surface; contacting the sensitizedsurface with an aqueous solution or mixture containing a silver salthaving a pH in the range from about 5 to about 10 to form a catalyzedsurface; and electroless plating the catalyzed surface by applying anelectroless plating solution to the catalyzed surface.

(5: Metal Plated Articles)

[Sports Articles]

Articles comprising metal-coated substrates made of plastics andcomposites are known in the prior art. Numerous articles, e.g., sportinggoods, automotive parts, industrial components that are lightweight areprone to failure by breakage. For instance, fishing rod tipfailure/breakage is a major cause of warranty returns of fishing rods tothe manufacturer. As golf clubs are swung in close proximity to theground, it is not unusual for the club head to strike the ground withconsiderable force, applying a large force or torque to the narrowestportion of the shaft, i.e. to the tip of the shaft that is joined to theclub head. This impact can cause failure of the composite shaft at thispoint, causing the tip of the shaft to break at or closely adjacent tothe club head.

Sandman in U.S. Pat. No. 5,538,769 (1969) describes a graphite compositeshaft with a reinforced tip, suitable for use in fishing rods or golfclubs. The shaft includes a base shaft made at least partially ofgraphite composite material provided in one or more layers or plies.These shafts have relatively slender tips that are normally prone toimpact damage. The reinforcement layer extends only part of the way upthe length of the base shaft and is intended to render the shaft moreresistant to impacts occurring at the tip thereby increasing thedurability of the shaft without decreasing the performance of thefishing rod or golf club that incorporates the shaft. The reinforcementlayer is applied by winding a suitable reinforcement tape around theouter periphery of the shaft.

Galloway in U.S. Pat. No. 6,692,377 (2004) describes an improved golfclub shaft made of a composite material, such as carbon/epoxy, and ametal foil wrapped in a spiral pattern around at least a portion of theshaft body. The metal foil increases the torsional stiffness of theshaft and improves its bending stiffness, thereby enabling the first andsecond frequencies of the golf club to remain in a desired range.

Palumbo in U.S. Ser. No. 11/013,456 (2004), assigned to the applicant ofthis application, describes articles for automotive, aerospace,manufacturing and defense industry applications including shafts ortubes used, for example, as golf club shafts, ski and hiking poles,fishing rods or bicycle frames, skate blades and snowboards that are atleast partially electroplated with fine-grained layers of selectedmetallic materials. Coated parts with complex geometry are described aswell. Alternatively, articles such as conical or cylindrical golf clubshafts, hiking pole shafts or fishing pole sections, plates or foils andthe like can also be electroformed fine-grained metallic materials on asuitable mandrel or temporary substrate yielding strong, ductile,lightweight components exhibiting a high coefficient of restitution anda high stiffness.

Yanagioka in U.S. Pat. No. 4,188,032 (1980) discloses a nickel-platedgolf club shaft made of fiber-reinforced material having onsubstantially its entire outer surface a metallic plating selected fromthe group consisting of nickel and nickel based alloys for the purposeof providing a wear-resistant coating. The electroless nickel coating ofchoice is 20 μm thick and the deposition time is 20 hrs, resulting in adeposition rate of 1 μm/hr.

Chappel in U.S. Pat. No. 6,346,052 (2002) discloses golf club irons withmultilayer construction. The golf club head comprises a soft nickelalloy core and a hard chrome coating. The process used to produce thegolf club heads involves an investment casting process in which the softnickel alloy core is cast and the hard chrome coating is electroplatedonto the core. Unlike the decorative chrome used on prior art golf clubs(hardness of about 35 to 45 Rockwell C, typical thickness between 0.05to 0.2 mil) the chrome outer layer used in the invention is between 0.8mils to about 1 mil (20 μm to 25 μm) thick, which is at least four timesthicker than conventional applications of decorative chrome in prior artclubs. The hard chrome plating employed provides durability withoutcompromising the superior feel characteristics of the relatively softnickel alloy core when a golf ball is struck.

Heinrich in U.S. Pat. No. 6,679,788 (2004) discloses a golf club headwhere at least part of the striking face is coated with alloys oftransition metals and metalloids with a hardness over 1,250 VHN by athermal spraying method with average spray-particle velocities of over500 m/s.

Although golf club heads and faceplates are primarily made of metal,polymeric materials can be used. In this context reference is made toPond, U.S. Pat. No. 5,524,331 (1996) that discloses a method for castinga graphite-epoxy resin composite insert within a recess of a face of ametal golf club head. The objective of this approach is directed atdisplacing the weight away from the center and increasing the moment ofinertia.

Schmidt in U.S. Pat. No. 5,485,997 (1996), discloses a golf putter headwith a face plate insert composed of a non-metallic material such as anelastomer to enlarge the sweet spot and improve the peripheralweighting.

Numerous publications describe sport racquets reinforced and stiffenedby structural straps or plates at the outer or inner surfaces, or withinthe wall of the handle and frame, including Stauffer (U.S. Pat. No.3,949,988 (1976), Matsuoka in JP2000061005 (1998) and JP09285569 (1996).

Reed in U.S. Pat. No. 5,655,981 (1997) describes a shaft for a hockeystick comprising a non-metallic material coated first by a layer of aresilient yet tough polymeric material, a second layer comprised of ametal including aluminum, copper, gold and silver and a third layercomprised of a clear, resilient, tough material. The thin metallic layeris applied to the substrate by a vapor vacuum deposition process. Thebase layer, metallic layer and top layer have an overall thickness ofless than 3 mils. The sole purpose of the thin metallic layer [maximumthickness of 0.01 mils (0.25 μm)], is to enhance the appearance.

[Polymer Ammunition Casings]

Burgess in U.S. Pat. No. 3,749,021 (1973) discloses a metal-platedplastic ammunition cartridge casing. A nickel or chromium metal film,preferably between 0.05 to 0.1 mils thick is plated onto a plasticcartridge case to increase the strength, abrasion and burn-throughresistance as well as lubricity of the cartridge casing. The plasticcasing may comprise a filled or a fiber reinforced plastic. A platedmetal skin preferably 5 to 7 mils thick may also be employed inconjunction with non-reinforced plastic casings to increase the strengthof the casing in selected areas.

Husseini in U.S. Pat. No. 6,845,716 (2005) discloses a molded plasticcartridge casing which is molded around at least a portion of theprojectile. ZYTEL® resin, a modified 612 Nylon® resin to increaseelastic response, available from E.I. DuPont De Nemours Co., and is aparticularly suitable material for the cartridge casing. The base may bea metal base, such as a brass base, a plastic material base, a ceramicbase, a composite base, or combinations thereof.

[Automotive Articles]

Various automotive articles made of plastics and composites optionallymetal coated for appearance and corrosion protection are known in theprior art. Exterior automotive parts, such as a front end grilles or awheel covers, generally contain thicker metal layers and are formulatedto withstand a more aggressive environment than interior automotiveparts or decorative parts for household appliances.

Wang in U.S. Pat. No. 6,010,196 (2000) describes a simulated chromeplated vehicle wheel formed by placing a thin, chrome plated wheel coverthat is preferably constructed of a plastic substrate over aconventional, non-plated vehicle wheel. The wheel cover has a contourand includes surface patterns that are identical to the contour andsurface patterns of the vehicle wheel thereby providing the appearanceof a solid chrome plated vehicle wheel.

Vander Togtin U.S. Pat. No. 4,999,227 (1991) discloses an automotivebumper comprising a shell of injection molded platable grade ABSplastic. The plastic shell is plated with chromium metal and thenbackfilled by injection of ethylene ionomers. The composite structurehas a pleasing metallic appearance, is lightweight, easy to manufactureyet has the structural integrity necessary to serve as impact resistantmembers on automobiles.

Luch in U.S. Pat. No. 4,429,020 (1984) describes metal-polymer compositearticles, e.g., knobs, nuts, trimmings or ornaments, automotivecomponents including grilles, headlamp bezels and surrounds, wheelcovers, trim, hubs and like parts, having silvery hued metal surfaces.Suitable directly electroplateable polymeric materials includepolyvinyls, polyolefins, polystyrenes, elastomers, polyamides andpolyesters and contain carbon black and sulfur. The surface of thepolymer is plated with an alloy of tin and Group VIII metals. A durableadherent Ni layer is disposed between the plastic body and the surfaceplating.

Anderson in U.S. Pat. No. 4,671,552 (1987) describes an improved grilleguard made of rigid plastic plates such as ABS and Al or steel tubes foruse on light truck-type vehicles, such as pickup trucks, vans andfour-wheel drive vehicles which is substantially lighter (perhapsone-third the weight) and substantially cheaper (perhaps one-third thecost) of a comparable steel unit, yet may be provided with an appearanceequivalent to a corresponding plated steel grille guard. The grilleguards include end plates which may be reinforced.

Buckley in U.S. Pat. No. 6,802,232 (2004) describes brake andaccelerator pedals for golf and utility vehicles made of molded plastic.The pedal arm assembly is injection molded such that the arm and thepedal member are integrally molded. The pedal arm assembly may includean internal reinforcement member that is encapsulated within the pedalarm assembly for improved structural rigidity.

Smith in U.S. Ser. No. 10/700,887 (2003) discloses a running board for apassenger car or light truck consisting of an upper molded thermoplasticsection having a Class A automotive finish and a lower section havingreinforcing ribs and mounting brackets. The upper section includes threelayers: a paint film having a Class A automotive finish, a thin layer ofthermoplastic polyolefin (TPO) and a thick layer of polypropylene. Thelower section is homogeneous and may be a plastic such as TPO,polypropylene or high-density polyethylene (HDPE), which may furthercontain chopped, randomly oriented glass reinforcing fibers. The twosections are secured to one another about their peripheries byautogenous bonding.

OBJECTS AND SUMMARY OF THE INVENTION

It is an objective of the present invention to provide strong,lightweight articles for use in sporting goods, automotive, aerospaceand industrial components, having a fine-grained structural metalliclayer on a polymeric substrate. The fine-grained metal, metal alloy ormetal matrix composite layer of high strength is applied to the polymersubstrate, e.g., by a suitable metal deposition process or alternativebonding means including gluing, to enhance the overallstrength-to-weight ratio, improve the damping characteristics and/or toprovide external or internal surfaces of high hardness, high resilience,high yield strength, high scratch and wear resistance, and appealingappearance.

It is an objective of the invention to provide fine-grained metallicmaterials for rendering articles strong, wear and abrasion resistant,and light-weight. It is an objective to synthesize the fine-grainedmetallic material by a convenient and cost-effective production processincluding electrodeposition, physical vapor deposition (PVD), chemicalvapor deposition (CVD), gas condensation and cold spraying techniques.

It is an objective of the invention to apply the fine-grained metalliccoating to at least part of the surface of an article made substantiallyof a filled or unfilled polymer material, e.g., a graphite fiber/epoxyresin composite, polyamide, glass filled polyamide, polyester,polythalamide, polypropylene, polycarbonate, polytetrafluoroethylene(PTFE), polyvinyl chloride (PVC) or acrylonitrile-butadiene-styrene(ABS). If required, the polymer substrate surface can be renderedconductive, e.g., by coating the surface with a thin layer of silver,nickel, copper or the like or a combination of any two or all of thesemetals by any number of suitable processes including chemical reduction(electroless plating or chemical reduction spray), thermal spraying,chemical vapor deposition, physical vapor deposition or by any two ormore of these. Alternatively, the intermediate conductive layercomprises polymeric materials with conductive particulates therein,e.g., conductive paints, conductive epoxy or polymeric adhesivematerials. The conductive particulates are composed of or contain Ag, Nior Cu or graphite or other conductive carbon or a combination of two ormore thereof.

It is an objective of the invention to pretreat the surface of thepolymeric substrate to achieve a surface roughness in the range ofRa=0.25 μm to Ra=25 μm prior to applying the fine-grained metalliccoating. In the context of this application the Average Roughness Ra isdefined as the arithmetic mean of the absolute values of the profiledeviations from the mean line and is by far the most commonly usedparameter in surface finish measurement.

It is an objective of this invention to provide a process capable ofapplying fine-grained metallic materials to tubes, shafts as well ascomplex-shaped articles.

It is an objective of this invention to provide shafts, tubes or othersuitable shapes for sporting goods, automotive and industrial componentsand the like that are lightweight, resistant to abrasion, resistant topermanent deformation and do not splinter when cracked or broken.

It is an objective of this invention to provide articles, including golfclub heads, golf club shafts, hockey sticks, lacrosse sticks, ski orhiking pole shafts, fishing poles, baseball/softball bats, tubes for usein bicycle frames, arrow shafts and polymer cartridge casings that areat least partially coated with or encapsulated by a fine-grainedmetallic layer.

It is an objective of this invention to provide articles that are atleast partially coated with or encased by a fine grained metallic layerhaving a yield strength of at least 300 MPa, preferably at least 500 MPaand more preferably at least 750 MPa.

It is an objective of this invention to provide articles that are atleast partially coated with or encased by a fine-grained metallicmaterial and are more than 5%, preferably more than 10%, more preferablymore than 20% and even more preferably more than 40% lighter thanconventional articles.

It is an objective of the invention to provide a golf club capable ofachieving increased flight distance performance, provide increasedcontrol over the club shaft and head and/or provide improved golf ballflying distance and accuracy characteristics, as well as improvedvibration damping characteristics at low overall weight.

It is an objective of this invention to providegraphite-fiber/epoxy-based arrow shafts that are at least partiallycoated with or encased by a fine-grained metallic layer and provideimproved stiffness and do not bend when hitting a hard object and thatprovide high specific strength yet remain lightweight enabling thearrows to achieve higher velocities and therefore delivering increasedkinetic energy upon impact.

It is an objective of this invention to provide lightweightpolymer-cased ammunition at reduced cost compared to conventionalbrass-cased ammunition which is suitable for use in repeating firearms.

It is an objective of this invention to at least partially coat or coverthe inner or outer surface of parts including complex shapes such asracquets (e.g. for tennis, squash, badminton, etc, baseball bats, skis,golf club face plates and/or heads) or other sporting equipment,automotive components (e.g. grille guards, brackets, running boards) andindustrial components with fine-grained metallic materials that arestrong, lightweight, have a high stiffness, resist deflection and havehigher natural frequencies of vibration, as well as display highresilience, while being manufactured by a convenient and cost-effectivemethod.

It is an objective of the invention to provide articles with strong,hard, fine-grained metallic materials that can be further strengthenedby applying a suitable heat treatment afterelectroplating/electroforming.

It is an objective of the invention to apply a fine-grained metal, metalalloy or metal matrix composite layer to at least part of the inner orouter surface of an article including a golf club head comprising aplastic substrate [e.g. acrylonitrile-butadiene-styrene (ABS),polyamides including Nylon®, thermoplastic polyolefins (TPOs),polycarbonate, e.g. injection or blow molded) in order to form a golfclub head with

-   -   (a) a high resilience face area, of light weight, and providing        increased driving distance for the golf ball;    -   (b) damping characteristics providing superior “sound” and        “feel” when e.g. striking a golf ball;    -   (c) high strength-to-weight ratio allowing strategic perimeter        weighting of the club head; and    -   (d) an external surface of high hardness for improved scratch        and wear resistance.

It is an objective of the invention to apply a fine-grained metal, metalalloy or metal matrix composite layer to at least part of the inner orouter surface of e.g. structural automotive components to achieve:

-   -   (a) increased strength to weight performance where a strong,        thin fine-grained coating allows the design of parts where space        is a constraint, replacing large bulky parts;    -   (b) improved stiffness where the lightweight fine-grained        coating imparts an improvement in bending stiffness and an        increase in natural vibration frequency, in many cases taking        advantage of shape factors with location of the metal shell        and/or coating;    -   (c) improved impact toughness, creep and fatigue performance;    -   (d) an external surface of high hardness for improved scratch        and wear resistance.

With a view to achieving these objectives and improving the propertiesof commercial articles, in particular sporting equipment, automotiveparts, aerospace and industrial components, the invention according toone embodiment provides an article with a fine-grained metal, metalalloy or metal matrix composite coating having an average grain sizebetween 2 nm and 5,000 nm, a thickness of between 25 μm and 5 mm and upto as much as 5 cm and a hardness between 200 VHN and 3,000 VHN. Thecoating exhibits a resilience of at least 0.25 MPa and up to 25 MPa andan elastic strain limit of at least 0.25% and up to 2.00%.

According to a further embodiment of the invention, fine-grainedelectroformed metallic components including foils, tapes and plates areprovided exhibiting an average grain size between 2 nm and 5 μm, ahardness between 400 VHN and 2,000 VHN and a yield strength of between200 MPa and 2,750 MPa. The fine-grained electroformed metalliccomponents are subsequently applied to and securely fastened to suitablepolymeric substrates.

Polymer/metal composite articles, such as shafts and tubes incorporatingthe fine-grained metallic coating representing at least 5%, preferablymore than 10% and even more preferably more than 20% and up to 75%, 85%or 95% of the total weight on a polymer substrate optionally containinggraphite/carbon fibers, are disclosed. The torsional or bendingstiffness per unit weight of the article containing the fine-grainedmetallic coating is improved by at least about 5% when compared to thetorsional stiffness of the same article not containing the metalliccoating.

GENERAL DESCRIPTION OF THE INVENTION

Suitable processes for producing or coating articles according to theinvention include electrodeposition, physical vapor deposition (PVD),chemical vapor deposition (CVD), gas condensation and cold sprayingtechniques.

In the case electrodeposition is used as the process for producingarticles and components of sporting equipment according to theinvention, it comprises the steps of, positioning the metallic ormetallized work piece or the reusable mandrel/temporary substrate to beplated in a plating tank containing a suitable electrolyte, providingelectrical connections to the mandrel/temporary substrate to be platedand to one or several anodes, forming and electrodepositing a metallicmaterial with an average grain size of less than 1,000 nm on at leastpart of the surface of the work piece using a suitable D.C. or pulseelectrodeposition (5-100% duty cycle) process described in DE 10,288,323(2005), assigned to the applicant of this application. DE 10,288,323 isincorporated herein by reference for its teaching of electrodepositiontechniques which may be used in the preparation of articles according tothe present invention.

Deposition rates required are at least 25 μm/h, preferably 50 μm/h andmore preferably greater than 75 μm/h.

Suitable metal deposition processes can be applied to establishhigh-strength coatings of pure metals or alloys of metals selected fromthe group of Ag, Al, Au, Cu, Co, Cr, Ni, Sn, Fe, Pt, Ti, W, Zn and Zrand alloying elements selected from Mo, W, B, C, P, S and Si and metalmatrix composites of pure metals or alloys with particulate additivessuch as powders, fibers, nanotubes, flakes, metal powders, metal alloypowders and metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Sn, V,and Zn; nitrides of Al, B, Si and Ti; C (graphite, diamond, nanotubes,Buckminster Fullerenes); carbides of B, Cr, Bi, Si, Ti, W; and selflubricating materials such as MoS₂ or organic materials, e.g., PTFE. Thesuitable processes can be employed to create high strength, equiaxedcoatings on metallic components, or non-conductive components thatoptionally have been metallized. In an alternative embodiment, the samemetal deposition processes can be used to form a stand-alone article ona suitable temporary substrate and, after reaching the desired platingthickness, to remove the free-standing electroformed article from thetemporary substrate and, in a subsequent step, apply it to the polymersubstrate through the use of suitable adhesives.

Suitable permanent polymeric substrates materials include filled orunfilled epoxy resin composites, polyamide, polyester, polythalamide,polypropylene, polycarbonate, polyvinyl chloride (PVC), thermoplasticpolyolefins (TPOs), polytetrafluoroethylene (PTFE) polycarbonate andacrylonitrile-butadiene-styrene (ABS). Suitable fillers include glassfibers, carbon, carbon nanotubes, graphite, graphite fibers, metals,metal alloys, ceramics and mineral fillers such as talc, calciumsilicate, silica, calcium carbonate, alumina, titanium oxide, ferrite,and mixed silicates. Mineral-filled, plating-grade polyamide resinscontaining powdered (e.g., 0.02-20 microns) mineral fillers such astalc, calcium silicate, silica, calcium carbonate, alumina, titaniumoxide, ferrite, and mixed silicates (e.g., bentonite or pumice) havingmineral contents of up to about forty percent by weight and providinghigh strength at relatively low cost are particularly suitablesubstrates. Suitable polyamides are available from a number of vendorsincluding Allied Chemical, Firestone, DuPont and Monsanto, to name afew. Other suitable substrates include acrylonitrile-butadiene-styrene(ABS) and thermoplastic polyolefins (TPO), available in “plating grades”and optionally reinforced by a variety of fillers including glass fiber.

The surface of the polymeric part as prepared by any suitable molding orforming operation is typically quite smooth and the surface roughnessRa<0.1 μm. To enhance the adhesion of the metallic coating the surfaceto be coated is roughened by any number of suitable means including,e.g., mechanical abrasion, plasma and chemical etching to achieve asurface roughness in the range of Ra=0.25 μm to Ra=25 μm.

The following listing describes suitable operating parameter ranges forpracticing the invention:

-   -   Metallic Layer Thickness Minimum: 25 μm; 30 μm; 50 μm    -   Metallic Layer Thickness Maximum: 5 mm, up to 5 cm    -   Minimum Average Grain Size Range: 2 nm, 5 nm    -   Maximum Average Grain Size Range: 1 μm, 5 μm    -   Minimum Hardness (VHN): 200; 300; 400    -   Maximum Hardness (VHN): 1,000; 2,000; 3,000;    -   Deposition Rate Range: 10-500 μm/hr    -   Yield Strength Range: 200 MPa to 2750 MPa    -   Minimum Modulus of Resilience of the    -   Fine-grained Metallic Layer: 0.25 MPa, 1 MPa, 2 MPa, 5 MPa, 7        MPa    -   Maximum Modulus of Resilience of the    -   Fine-grained Metallic Layer: 12 MPa, 25 MPa    -   Elastic Limit Range: 0.25%-2.00%    -   Particulate Content Range: 2.5% to 75% by Volume    -   Fatigue resistance: TBD    -   Minimum Substrate Surface Roughness [Ra (μm)] 0.25, 0.4, 0.5, 1    -   Maximum Substrate Surface Roughness [Ra (μm)] 5, 10, 25

The fine-grained metallic materials of the present invention optionallycontain at least 2.5% by volume particulate, preferably at least 5% andup to 75% by volume particulate. The particulate can be selected fromthe group of metal powders, metal alloy powders and metal oxide powdersof Ag, Al, Co, Cu, In, Mg, Ni, Si, Sn, Pt, Ti, V, W and Zn; nitrides ofAl, B, Si and Ti; C (graphite, carbon, carbon nanotubes, or diamond);carbides of B, Cr, Bi, Si, Ti, W; MoS₂; ceramics, glass and organicmaterials such as PTFE and other polymeric materials (PVC, PE, PP, ABS).The particulate average particle size is typically below 10,000 nm (10μm), 5,000 nm (5 μm), 1,000 nm (1 μm), and more preferably below 500 nm.

The present invention provides for applying fine-grained metallicmaterials having a thickness of at least 0.025 mm, preferably more than0.030 mm, more preferably more than 0.05 mm and even more preferablymore that 0.1 mm to the surface of appropriate articles. Suitablearticles include sporting goods such as golf club heads, inserts forgolf club heads, face plates for golf clubs; shafts for golf clubs,hockey sticks, hiking and skiing poles, fishing poles, arrows etc. andarticles with complex shapes such as baseball bats, skate blades, snowboards and tennis rackets. Suitable automotive articles includegrill-guards, brake, gas or clutch pedals, fuel rails, running boards,spoilers, muffler tips, wheels, vehicle frames, structural brackets.

The fine-grained metallic materials of this invention have an averagegrain size under 5 μm (5,000 nm), preferably under 1 μm (1,000 nm),preferably in the range of 2 to 750 nm, more preferably between 10 and500 nm and even more preferably between 15 nm and 300 nm.

The fine-grained metallic materials of this invention have a modulus ofresilience of at least 0.25 MPa, preferably at least 1 MPa, morepreferably at least 2 MPa, more preferably at least 5 MPa and even morepreferably at least 7 MPa and up to 25 MPa.

The fine-grained metallic materials of this invention have an elasticlimit of at least about 0.75%, and preferably greater than about 1.0%;and preferably greater than 1.5% and up to 2.0%.

To ensure part reliability, it is preferable to maintain the averagethickness to average grain size ratio of the fine-grained metallicmaterial layer at a minimum value of 10, preferably greater than 500,and more preferably greater than 1,000; and up to 1,250,000 and as muchas 25,000,000.

In a preferred embodiment of the process of this invention, dispersionstrengthening of the fine-grained metallic materials is performed by asubsequent heat-treatment.

According to this invention, patches or sections can be formed onselected areas of the polymeric substrate, without the need to coat theentire article.

According to this invention patches or sleeves of the fine-grainedmetallic materials are not necessarily uniform in thickness and can beapplied in order to e.g. enable a thicker deposit on selected sectionsor sections particularly prone to heavy use such as golf club faceplates, the tip end of fishing poles and shafts for golf clubs, skiingor hiking poles etc.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to better illustrate the invention by way of examples,descriptions are provided for suitable embodiments of themethod/process/apparatus according to the invention in which:

FIG. 1 is a picture of a cross-sectional view of a n-Ni coating appliedto a graphite/epoxy hybrid golf shaft.

FIG. 2 is a picture of a polymer ammunition casing (0.233 caliber) thathas been reinforced by a layer of fine-grained Ni-20Fe, after firing.

FIG. 3 is an image of a 5 mm thick n-Ni—P/epoxy laminate produced toform thick (>5 mm) laminated assemblies.

FIG. 4 is a picture of a n-Ni-10Fe adhesive tape applied to a tubularautomotive part.

FIG. 5 shows a plastic grille-guard for a truck containing afine-grained metallic coating to add stiffness. (6 mm plastic with0.001″ n-Ni-20Fe coating)

FIG. 6 shows the deflection of the plastic grill-guard containing afine-grained metallic coating with a 250 lb load applied at the crossbeam. (Target deflection: <25 mm; Performance 24.6 mm)

FIG. 7 shows sections of nanocoated-PC/ABS (left) and stainless steel(right) automotive running board parts.

The present invention is intended for depositing fine-grained metallicmaterials onto articles in the form of external or internal coatings orelectroforming fine-grained metallic materials comprising a metal oralloy selected from Cu, Co, Cr, Ni, Fe, Sn, Mo and Zn optionally withparticulate dispersed in the fine-grained layer and subsequentlyapplying the fine-grained metallic materials to the substrate.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENT

This invention relies on producing fine-grained, coatings by suitablemetal deposition processes including DC or pulse electrodeposition.

The person skilled in the art of plating, in conjunction e.g. with U.S.Pat. No. 5,352,266 (1994), U.S. Pat. No. 5,433,797 (1995) and in DE10,288,323 (2005) U.S. Ser. No. 10/516,300 (2002) and WO2004/001100 A12002] cited already, will know how to electrodeposit selectedfine-grained metals or alloys by selecting suitable plating bathformulations and plating conditions. These patents are incorporatedherein by reference for their disclosure of electrodeposition methods.Optionally, solid particles can be suspended in the electrolyte and areincluded in the deposit as described in DE 10,288,323 (2005).

The person skilled in the art of PVD, CVD and cold spraying will alsoknow how to deposit selected fine-grained metallic layers on suitablesubstrates.

Minimizing the weight of articles, which is desirable for numerousapplications, can be achieved by increasing the strength of the metallicmaterials by grain-size reduction. Depending on the ductility required,the grain size of e.g. Ni-based coatings in the range of 2 nm to 5,000nm, preferably 10 nm to 500 nm provide suitable mechanical properties.

Depending on the requirements of the particular application, thematerial properties can also be altered, e.g., by incorporating drylubricants (such as MOS₂ and PTFE), abrasion or wear resistantparticles. Incorporating a sufficient volume fraction of particulate cantherefore be used to further enhance the material properties. Generally,the particulates can be selected from the group of metal powders, metalalloy powders and metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Snand Zn; nitrides of Al, B, Si and Ti; C (graphite, diamond, nanotubes,and/or Buckminster Fullerenes); carbides of B, Si, Ti, W; selflubricating materials such as MoS₂, organic materials such as PTFE andpolymeric materials.

As noted above, particularly suited applications for the fine-grainedmetallic materials disclosed herein include golf shafts, ski poles,fishing rods, hockey sticks, tennis racquets, bicycle frames and otherarticles and structures comprised of conventional metal, polymer orgraphite composites that are coated on at least part of the interiorand/or exterior surfaces, or, alternatively are net-shape formed withthe use of a temporary substrate and subsequently applied to thepermanent substrate. Conventional metals e.g. aluminum, copper, nickeland their alloys are relatively soft, permanently deform and breakeasily as a result of the bending and torsional loads encountered duringuse. Furthermore, these materials with conventional grain-sizes above 10μm, generally exhibit a low resistance to abrasion and cut or scratcheasily and can benefit from the fine-grained metallic layer described inthis invention. Shafts made from composites of synthetic resins andfilaments are more resilient under bending forces than aluminum, butlack sufficient strength. This deficiency, however, can be overcome byapplying a fine-grained metallic layer according to the presentinvention.

The rebound distance of an object, e.g. a golf ball, tennis ball,baseball or the like when it impacts a certain material is a function ofthe modulus of resilience, U_(r), of the material, which is expressedas:

$U_{r} = {{\frac{1}{2}\sigma_{y}ɛ_{y}} = \frac{\sigma_{y}^{2}}{2\; E}}$

(Metals Handbook, Ninth Edition, Volume 8, Mechanical Testing, AmericanSociety for Metals, Materials Park, Ohio, 44073)

Where ∈_(y) is the maximum true strain at the yield point, σ_(y)represents the yield strength and E the modulus of elasticity. Asfine-grained materials described in this invention possess yieldstrength values, σ_(y), which are three to five and up to ten timesgreater that those of conventional coarse-grained metals, the resilience(rebound distance capacity) can therefore be increased nine to twentyfive-fold and up to hundred fold. The modulus of elasticity E, however,is typically not affected by reducing the grain size of a given metallicmaterial, provided the material is fully dense. The modulus ofelasticity, however, can be altered e.g. by using metal matrixcomposites.

Material properties required for a number of applications also include ahigh elastic strain-to-failure limit. Low damping characteristics (lowabsorption and high re-release of energy) ensure that even after highload and stress deformation the material springs back to its originalshape as required on strike faces, e.g., in selected automotiveapplications or sporting goods such as golf head face plates andbaseball bats. Conventional metals have elastic strain limits of 0.65%or less. The current invention is directed to metallic materials havingelastic limits of at least about 0.75%, preferably greater than about1.0%; and preferably greater than 1.5% and up to 2.0%.

FIG. 1 is a picture of a cross-sectional view of a n-Ni coating appliedto a graphite/epoxy golf shaft. Carbon fiber composites possess muchhigher specific rigidity and lower density than steel; however, thelight-weight, carbon-fiber golf exhibits undesirable twisting of theclub head relative to the shaft on down-swing and particularly at ballcontact, resulting in poor accuracy and flying distance. This limitationcan be overcome by coating at least 10% of the composite shaft'sexternal and/or internal surface with the fine-grained metallic layerdescribed.

FIG. 2 is a picture of a polymer ammunitions cartridge with a base thathas been reinforced by a layer of fine-grained Ni-20Fe. The fine-grainedmetallic material layer provides high strength and a low coefficient offriction.

FIG. 3 is an image of a 5 mm thick n-Ni—P/epoxy resin laminate producedto form thick (>5 mm) laminated assemblies according to one preferredembodiment.

FIG. 4 is a picture of an n-Ni-10Fe adhesive tape applied to a tubularautomotive part. As will be described in greater detail below, thisfine-grained metallic layer can be applied as an adhesive tape to atleast part of polymer article.

FIG. 5 shows a plastic grill-guard for a truck containing a fine-grainedmetallic coating (n-Ni-20Fe) to add stiffness. This part is blow-moldedin PC/ABS and with plastic alone, does not meet the deflection andvibration requirements for the application. The performance requirementscan be met by adding the stiff, lightweight fine-grained metalliccoating.

FIG. 6 shows the deflection encountered by the plastic grille-guardcontaining the fine-grained metallic coating with 250 lbf applied at thecross-beam to be 24.6 mm which meets the requirement of a maximumdeflection of 25 mm.

FIG. 7 shows sections of nanocoated-PC/ABS and stainless steelautomotive running board parts.

Various non-metallic materials are now commonly used in the manufactureof sporting goods, automotive components, aerospace parts or industrialarticles and include polymeric resin matrix composites employingmaterials including carbon fibers, ceramic matrix, aramid fibers,polyethylene fibers, boron, fiberglass, and various thermoplasticsincluding, but not limited to, polypropylene, polyethylene, polystyrene,vinyls, acrylics, nylon and polycarbonates, among others.

As highlighted a number of processes can be used to apply thefine-grained metallic material to the polymer substrates. In the case ofPVD, CVD, cold spraying or the application of an adhesive fine-grainedmetal tape, the surface of the substrate may not require anypretreatment. If electroplating is used to apply the fine-grainedmetallic material a good bond can be achieved when suitably rougheningthe surface of the substrate. Non-conductive polymer substrates can berendered suitable for electroplating by applying a thin layer of aconductive material e.g. by electroless deposition, physical or chemicalvapor deposition, or applying electrically conductive paints by variousmeans. It should be clear to those skilled in the art that the subjectinvention encompasses the use of virtually any substrate material.

According to a further preferred embodiment of the present invention, itis also possible to produce fine-grained coatings by electroplatingwithout the need to enclose the area of the article to be coated andform a plating bath around it. Selective brush or tampon plating is asuitable alternative, particularly when only a small portion of thework-piece is to be plated. The brush plating apparatus typicallyemploys a dimensionally stable or soluble anode wrapped in an absorbentseparator felt to form the anode brush. The brush is rubbed against thesurface to be plated in a manual or mechanized mode and electrolytesolution containing ions of the metal or metal alloys to be plated isinjected into the separator felt.

Preferred Embodiments

The following examples describe specific features of selectedembodiments of the invention to illustrate and provide a description forthose of ordinary skill in the art.

Example 1 Fine Grained Metallic Material Properties

As highlighted, fine-grained materials can be formed using a variety ofmanufacturing techniques, such as sputtering, laser ablation, inert gascondensation, oven evaporation, spray conversion pyrolysis, flamehydrolysis, high energy milling, sol gel deposition, electrodeposition,physical vapor deposition, chemical vapor deposition and cold spraying.According to selected embodiments of the invention, electrodepositionand cold spraying are particularly desirable, since these coatingtechniques can be used to form nanostructured materials ecomomically athigh production rates. Table 1 list a number of fine-grained materialsavailable from Integran Technologies Inc. of Toronto, Canada(www.integran.com).

TABLE 1 Tensile Data for Various Nanocrystalline Metals and AlloysProduced by Integran Technologies Inc. YIELD AVERAGE STRENGTH ULTIMATETENSILE ELASTIC GRAIN SIZE INTERNAL (0.2%) STRENGTH LIMIT MATERIAL [nm]STRESS [MPa] [MPa] [%] Nano-Ni 100 (Compressive) 690 1100 0.37 Nano-Ni15 (Compressive) >900 >2000 0.49 Nano-Ni 10 w % Fe 20 Low-Med 1100 16000.59 (Tensile) Nano-Ni 20 Low-Med 1800 2300 0.97 20 wt % Fe (Tensile)Nano-Ni 40% Fe 20 Low-Med 1200 1700 0.65 (Tensile) Nano-Ni 50 wt % Fe 20Low-Med 1100 1500 0.59 (Tensile) Nano-Ni 60% Fe 20 Med-High 800 14000.43 (Tensile) Nano-Co2-3% P 15 Med-High 1000-1200 1300-1700 0.52(Tensile)

Measurements of mechanical characteristics of a number of materialsincluding metals, alloys and laminates of fine-grained coatings withpolymeric materials were made in accordance with standard protocols.Commercial reference materials are listed as well including carbonfibers, various steels, aluminum and titanium. The remaining materialsinclude fine-grained materials as well as selected hybrid materialscomprising laminates of fine-grained materials and polymeric materials.Specifically to fine-grained materials the properties for n-Ni andn-Ni-20Fe are listed having an average grain size of about 20 nm. Table2 compares the mechanical properties of a number of conventional metals,fine-grained Ni metal, fine-grained Ni—Fe alloy, along with laminatescomposed of fine-grained Ni—Fe alloy material and polymeric materials(graphite-fiber/epoxy, ABS or Nylon) as produced by IntegranTechnologies Inc. The mechanical characteristics of fine-grainedmaterials and fine grained metal/polymeric hybrid materials render themparticularly suitable for numerous commercial applications including,but not limited to, automotive parts, sporting goods, aerospace anddefense application and the like requiring a relatively high strength(e.g., in terms of yield strength and ultimate tensile strength), arelatively high strength-to-weight ratio (e.g., in terms of specificstrength), a relatively high resilience (e.g., in terms of modulus ofresilience), a relatively high elasticity (e.g., in terms of elasticlimit), a relatively high hardness, a relatively high ductility (e.g.,in terms of tensile strain-to-failure), and a relatively high wearresistance (e.g., in terms of Taber Wear Index).

Fine-grained Ni, fine-grained Ni—Fe alloys as well as composites offine-grained Ni—Fe alloys with suitable polymers containing thefine-grained metal to between 5-90% of the total weight of the laminateprovide “tailor made” superior mechanical properties making themparticularly suitable substitutes for metallic components in numerouscommercial applications as further illustrated in Table 2.

TABLE 2 Mechanical Property Comparison for Various Materials Ranked inRelation to Specific Strength. Strength to Yield Density, Strength,Density, [MPa * Material [MPa] [kg/m³] m³/kg] Carbon Fiber 1900 1.5 1267Tool Steel CPM 10V (grain size < 1980 7.4 268 10 μm) Fine-grained80Ni—20Fe (grain size 1785 8.6 208 20 nm) 20% fine-grained 80Ni—20Fe and577 2.88 200 80% (55% Graphite- fiber/45% epoxy) Tool Steel 40CrMo5(grain size > 1520 7.7 197 10 μm) 10% fine-grained 80Ni—20Fe and 4262.17 197 90% (55% Graphite- fiber/45% epoxy) 55% Graphite-fiber/45%epoxy 275 1.45 190 sheet molding material 50% fine-grained 80Ni—20Fe and904 4.8 188 50% ABS Composite Aluminum 7065 T6 (grain size > 500 2.7 18510 μm) 5% fine-grained Ni and 95% (55% 306 1.82 168 Graphite-fiber/45%epoxy) 30% fine-grained 80Ni—20Fe and 551 3.3 167 70% ABS CompositeStainless Steel AISI 440C (grain 1280 7.8 164 size > 10 μm) 20%fine-grained 80Ni—20Fe and 413 2.9 142 80% Nylon 66, glass reinforcedComposite Alloy Steel 34CrNiMo4 (grain size > 1103 7.8 141 10 μm) 10%fine-grained 80Ni—20Fe and 198 1.8 111 90% ABS Composite Titanium IMI834 (grain size > 500 4.6 109 10 μm) Aluminum 6061 T6 (grain size > 2752.7 102 10 μm) Fine-grained Ni (grain size 20 nm) 900 8.9 101 5%fine-grained 80Ni—20Fe and 156 1.9 82 95% Nylon 66, glass reinforcedComposite 5% fine-grained 80Ni—20Fe and 110 1.4 78 95% ABS CompositeAluminum 356.0-T6 (grain size > 165 2.7 62 10 μm) Iron A-536 (grainsize > 10 μm) 310 7.1 44 Stainless Steel 304 (grain size > 215 7.1 30 10μm) Nylon 66, glass reinforced 70 1.5 47 ABS 22 1.0 22 ConventionalNickel (grain size > 103 8.6 12 10 μm)

Example 2 n-Ni Coated Graphite Epoxy Golf Shaft 25% Ni

Penley™ graphite epoxy Light LS S-Flex and Penley™ G2-85 X-Flex graphiteepoxy shafts were used. The S-Flex shafts were characterized, strippedof the paint. The surface of the shafts was mechanically abraded usingsand blasting to a surface roughness of Ra=2.1 μm and subsequentlyplated with coarse and fine-grained coatings. Plated S-Flex shafts andunplated X Flex shafts having a total overall weight of 89 g wereperformance tested. The Ni sleeves were applied to the outside of theS-Flex graphite golf club shafts (OD₁=0.586″, tapering down toOD₂=0.368″ over a length of 40.5″) by electrodeposition in a modifiedWatts nickel bath and using a Dynatronix (Dynanet PDPR 20-30-100;www.dynatronix.com) pulse power supply. The starting mass of each S-Flexshaft was 71.5 g and prior to electroplating approximately 6.0 g ofpaint was stripped off. The coating procedure comprised three steps,namely (1) a thin electroless nickel plating to enhance the electricalconductivity using a procedure and chemicals provided by MacDermidIndustrial Products (www.macindustrialproducts.com) to achieve anaverage metal film thickness of 0.4 micron at a deposition rate of 1.7μm/hr and (2) electroplating to form the fine-grained or coarse-grainedcoating by varying the duty cycle and the peak current density. Theelectrolyte composition was 300 g/l nickel sulfate, 45 g/l nickelchloride, 45 g/l boric acid (H₃BO₃), 2 g/l saccharin and 3 ml/l NPA-91.Standard levelers and brighteners were employed and Inco nickel“R”-rounds were used as anode material. The weight of the metal coatingwas approximately 20 g. The electroplating conditions and metallic layerproperties used are summarized in Table 3. FIG. 1 provides a picture ofa cross-sectional view of the n-Ni coating applied to a graphite/epoxygolf shaft.

TABLE 3 Electroplating Conditions Fine Coarse Grained Grained DepositionTemperature [° C.] 60 60 Duty Cycle [%] 25 100 Deposition Rate [μm/hr]50 8.6 Average Coating Thickness: [μm] 55 58 Average Grain Size: [μm]0.025 10 Ratio Coating Thickness/Grain Size 2,200 5.8 Yield Strength[MPa] 900 276 Hardness [VHN] 580 140

Flexural stiffness was measured with a GolfSmith™ Frequency Analyzer andthe frequency was converted to a FlexRating (S=stiff, X=extra stiff).The torque values were determined using a GolfSmith™ Torque Arm with 1ft.lb torque 2″ from the tip end of the shaft. The data are summarizedin Table 4 and indicate that a significant improvement in the torquevalues can be obtained by replacing some fraction of the original weightof a graphite shaft with an electrodeposited coating, while maintainingthe overall total weight.

Professional golfers also tested these golf clubs. The feedback receivedsuggested that the clubs made according to this invention exhibited asuperior feel when compared to conventional graphite or steel shafts.Furthermore, the fine-grained coated graphite shafts performed unlikeeither conventional graphite or steel shafts. Compared to graphite, theball trajectory was reported to more consistent, as expected from thesignificantly improved torque value measurements.

TABLE 4 Comparison of Golf Shaft Properties Standard Graphite FineCoarse Shaft ID Shaft Grained Grained Graphite Shaft Weight 88.5 71.671.8 Before Coating [g] Deflection Before Coating X S S Torque BeforeCoating [°]  4.4  5.4  5.1 Plating weight [g] N/A 19.2 20.0 Total weight[g] 88.5 88.8 89.8 Deflection After Coating X X X Torque After Coating[°]  4.4  3.6  4.0

Similar performance benefits are achieved when the coated articles werefishing rods, hockey sticks, baseball bats, tennis racquets, bicycleframes and the like as well as automotive, aerospace and otherindustrial components.

Example 3 n-Ni Coated Graphite Epoxy Golf Shaft 5-90% Ni

Example 2 illustrates the benefit of relatively thin, fine-grainedmetallic coatings with a thickness of >25 μm and a fine-grained metalcontent of about 22% of the total weight. To investigate the effect offurther increasing metal content, hybrid graphite epoxy/metal golfshafts were prepared and characterized. True Temper Prolaunch™ (A-Flex)driver graphite epoxy shafts were mechanically abraded usingScotch-Brite® to an average surface roughness of Ra=1.7 μm andsubsequently coated with fine-grained metallic nickel layers of varyingweights. The process and the characterization techniques employed aredescribed in Example 2. Table 5 shows the torsional stiffness as afunction of the metal content of graphite/metal composite golf shafts.The data reveal that the torsional stiffness per unit weight of thearticle containing a metallic coating representing 5% of the totalweight is improved by at least about 5% when compared to the torsionalstiffness of the same article not containing the metallic coating.Further improvements in the torsional stiffness are obtained when therelative metal content of the hybrid shaft is further increased at arate of approximately one percent improvement in torsional stiffness perpercent relative metal content.

The torque and deflection data indicate that a significant performanceimprovement can be obtained by increasing the relative metal weight ofthe composite graphite epoxy/metal shafts. Graphite/metal composite golfshafts incorporating a metallic coating representing at least 5%,preferably more than 10% and even more preferably more than 20% of thetotal weight provide a substantial improvement over the performance ofuncoated graphite shafts.

Similar performance benefits were achieved when the coated articles werefishing rods, hockey sticks, baseball bats, Lacrosse sticks, tennisracquets, bicycle frames and the like as well as automotive, aerospaceand other industrial parts.

TABLE 5 Torsional Stiffness Comparison of Shafts Metal Content RelativeChange in Torsional of Hybrid Shaft Stiffness per Unit Weight [% [Weight% n-NiFe] per degree/kg] 0 0 5 6 25 30 43 55 55 70 68 83 75 95

Example 4 Arrow Shafts; NiFe on Graphite/Epoxy-Brush Plating

Over time a number of articles including archery arrows, baseball bats,hockey and Lacrosse sticks, bowling pins progressed from being made outof wood to aluminum. Specifically to e.g. arrows, aluminum arrows areabout 25% lighter than cedar wood arrows but with repeated use aluminumarrows tend to bend causing inconsistent trajectories and loss inaccuracy. More recently graphite composite arrows appeared, made fromcarbon fibers/polyvinyl or polyester resins. Graphite composite arrowsare lighter and tougher than aluminum and they do not bend when strikinga hard object. The lighter weight also leads to increased speedresulting in delivering higher kinetic energy on impacting the target.State of the art graphite composite arrows, however, also have a numberof limitations. They tend to oscillate along the shaft, which causesinaccuracies in flight and reduced penetration after hitting game. Dueto the relatively limited “spine weight” and their low stiffness, it isdifficult to use them with bows with more than 50 lb draw weight.Furthermore, upon penetrating the target the friction generated heats upthe tip section of the shaft to a temperature of over 150-200° C., whichis significantly above the maximum temperature the graphite fiber/epoxyresin composite is able to withstand, resulting in degradation of thegraphite fiber/epoxy resin composite shaft, deterioration of itsperformance and ultimately failure of the shaft.

To demonstrate the performance of composites made of fine-grainedmetallic materials with polymers selected 30″ arrows were used including⅛″ outer diameter graphite-epoxy/fiberglass arrows and 3/16″ outerdiameter Aluminum cored graphite-epoxy/fiberglass arrows. To improve theshaft performance and reduce the impact damage the test shafts werereinforced with an outer layer (thickness: 4 mils) of a fine-grainedNi-20Fe alloy around the tip section after mechanically abrading thesurface to be plated with Scotch-Brite® to an average surface roughnessof Ra=0.6 μm. The reinforcement layers extended part of the way (e.g.4″) or all the way up the length of the base shaft making the shaft moreresistant to impacts and thus increasing its durability.

The brush plating procedure described in U.S. Ser. No. 10/516,300 wasfollowed for coating arrow shafts with fine-grained Ni-20Fe with anaverage grain size of 20 nm using a selective plating unit supplied bySifco Selective Plating (www.brushplating.com). A DC power supply wasemployed. Standard substrate cleaning and activation procedures providedby Sifco Selective Plating were used. After the portion of the shaft tobe plated was abraded and metallized by silver spraying, a fine-grainedNi-20Fe layer was plated onto the outside casing from the base tobetween about half to the entire overall length by mounting the shaft ina rotator which also provided for the electrical contact to themetallized layer. A graphite anode brush wrapped in a suitable absorberwas brought into contact with the rotating arrow to deposit thefine-grained Ni-20Fe layer (average grain size 20 nm). The electrolytewas a modified Watt's bath for nickel containing 300 g/l nickel sulfate,45 g/l nickel chloride, 45 g/l boric acid (H₃BO₃), 2 g/l saccharin and 3ml/l NPA-91. To form the desired n-Ni-20Fe alloy 12 g/l FeCl₂.H₂O, 81g/l FeSO₄.7H₂O and 9 g/l Na-Citrate were added to the modified Wattsbath. Standard levelers and brighteners were employed. The n-Ni20Fe wasdeposited using DC (100% duty cycle) at a current density of 100 mA/cm²and 60° C.

Test samples were prepared with the fine-grained Ni-20Fe coatingrepresenting between 5 and 50% of the total arrow weight. The shaftswere fitted with field tips, nocks and suitable vanes and submitted totests using a compound bow with a draw weight of 60 lb. Overall thearrows containing the fine-grained metallic coating consistentlyoutperformed the uncoated arrows. Samples with a fine-grained metallayer of at least 5% of the total weight of the arrow displayed aperformance superior to that of conventional graphite fiber/epoxy andaluminum arrow shafts. Reinforcing the arrow shaft in the tip section(2″ to 8″) with a 0.001″-0.008″ thick fine-grained coating provedparticularly beneficial.

Example 5 Polymer Ammunition Casings NiFe on Glass-Filled Nylon

Ammunition containing plastic components including polymer cartridgecasings are known but to date have not been produced economically incommercial quantities with acceptable safety and consistent ballisticcharacteristics. Lightweight, polymer-cased ammunition utilizingstandard projectiles, primers, and propellants have the potential tosignificantly reduce the weight of ammunition. Deficiencies encounteredto date include:

-   -   the possibility exists that the projectile can be pushed into        the cartridge casing or fall out;    -   moisture uptake and sealing problems can occur failing to keep        the propellant dry;    -   a poor fit in the chamber can cause problems with inconsistent        projectile accuracy due to the variation in the gas pressure        during firing;    -   during the residence time of the cartridge in the weapon (after        chambering and before firing) the cartridges can be exposed for        some time to high temperatures of up to 200 or even 300° C.,        e.g., in automatic weapons which can degrade the polymer;    -   when fired plastic casings can permanently deform or provide        insufficient elastic spring back causing difficulties during        extraction;    -   portions of the polymer cartridge casing can break off or        disintegrate upon firing;    -   problems can be encountered with ease and reliability of spent        polymer cartridge extraction requiring a metal base or a metal        insert;    -   jamming in automatic weapons can occur particularly during        ejection of the casing;    -   insufficient lubricity of the casing fails to ensure reliable        extraction and ejection; and    -   excessive cost can be incurred due to complex designs and        manufacturing processes required.

To demonstrate the performance of composites made of fine-grainedmetallic materials with polymers 5.6 mm (0.223 caliber) polymerammunition casings made of Zytel®, a type 66 polyamide containing 40%glass filler, were used and were reinforced with a fine-grained metalliclayer. Prior to plating, the outside diameter of the casing to be platedwas reduced to accommodate 0.001″ to 0.010″ thick coatings withoutchanging the outer diameter. The average surface roughness wasdetermined to be Ra=0.5 μm. No adjustments were made to the innerdiameter of the casing in case the inside surface was plated. Theelectrolyte described in Example 4 was used for coating all the polymerammunition casings with fine-grained Ni-20Fe with an average grain sizeof 20 nm. Inco Ni “R” rounds and electrolytic iron chips were used asanode material in a typical tank plating set up. The portion of thecasing not to be plated was masked off and the area to be platedmetallized by silver spraying. The casing was mounted in a suitableholder and submersed into the plating tank. The fine-grained Ni-20Felayer was plated onto the outside casing from the base to between abouthalf to the entire overall length while the casing was rotated in thetank using DC (100% duty cycle) at a current density of 100 mA/cm² at60° C. Test samples were prepared with the fine-grained Ni-20Fe coatingrepresenting between 5 and 50% of the total casing weight. The casingswere fitted with primers, suitable powder charges and 55 grain FMJprojectiles and submitted to test firing in an M-16 weapon. Theperformance of the cartridges with respect to chambering, ejecting andaccuracy was monitored. Spent casings were examined with respect totheir mechanical integrity and signs of disintegration/cracking. Cracksand signs of polymer disintegration were observed frequently in theuncoated casings. Depending on the coating thickness used, cracks anddisintegration of the polymer was observed. Cracks in the fine-grainedcoating were at times noted, too, typically initiated in the extractorgroove, where the coating was the thinnest. Overall, the casingscontaining the fine-grained metallic coating consistently outperformedthe uncoated casings. Samples with a fine-grained metal layer of atleast 5% of the total weight of the casing displayed a performanceequivalent to that of conventional brass casings. The overall weight ofthe casings containing fine-grained coatings displaying acceptableoverall performance was reduced by between 10 and 75% when compared tobrass cartridges. Benefits in reliability and performance of themetal-polymer hybrid casings were observed irrespective of whether thecasing was coated on the outer surface, the inner surface or both.Reinforcing the casing near the base as illustrated in the sample shownin FIG. 2 proved particularly beneficial.

Example 6 n-Ni Coated ABS 5-90% NiFe

Suitable materials for use in golf heads include thermoplasticelastomers including styrene co-polymers, co-polyesters, polyurethanes,polyamides, olefins and vulcanates. Suitable thermoset polymers includeepoxides, polyimides and polyester resins. In this experiment a 1 mmthick faceplate made of a platable ABS chemically etched using asulfuric-acid/chromic-acid solution. The average surface roughness wasdetermined to be Ra=0.45 μm. After metallizing using the chemicalAg-spray the coupons were plating using a conventional tankelectroplating cell setup and employing the Watts bath as described inExample 2 to deposit a 0.4 mm thick layer of fine-grained nickel on onesurface. The nickel-layer surface was polished to a “mirror finish”ultimately using 1 μm diamond paste. A sample containing a 0.4 mm thicklayer of conventional coarse-grained nickel was prepared as described inExample 2. The two samples were suitably mounted on a horizontal plateand a steel ball (3 mm diameter) was dropped from a height of 60 cm ontothe samples. The rebound height was determined to be 2.9 mm for theconventional nickel layer, while the rebound height of the fine-grainednickel sample was determined to be 28.8 mm. The rebound height off thefine-grained Ni-sample improved by a factor of approximately 10, asexpected based on the 10 fold improvement in resilience (Table 6).

TABLE 6 Electroplating Conditions This Invention Prior Art (finegrained) (coarse grained) Average Coating Thickness: [micron] 400 400Average Grain Size: [μm] 0.025 20 Ratio Coating Thickness/Grain Size16,000 20 Deposition Rate [μm/hr] 45 18 Duty Cycle [%] 25 100 DepositionTemperature [° C.] 60 60 Yield Strength [MPa] 900 276 Resilience, MPa1.93 0.18 Rebound height [cm] 28.8 2.9 Improvement in Rebound Height [%]893 0

Example 7 n-Co—TiO2 Faceplates MMC on Polyurethane

A nanocrystalline Co—TiO₂ nanocomposite of 0.12 mm average coatingthickness was deposited onto a number of polyurethane golf headfaceplates from a modified Watts bath for cobalt using a soluble anodemade of electrolytic cobalt pieces and a Dynatronix (Dynanet PDPR20-30-100) pulse power supply. The electrolyte used comprised 300 g/lcobalt sulfate, 45 g/l cobalt chloride, 45 g/l boric acid, 2 g/lsaccharin and 4 ml/l NPA-91. Suspended in the bath were 0-500 g/ltitania particles (<1 μm particle size) with the aid of 0-12 g/l Niklad™particle dispersant (MacDermid Inc.). The electroplating conditions andmetallic layer properties used are summarized in Table 7. Prior toelectroplating the polyurethane substrate surface was mechanicallyabraded using Scotch-Brite®to an average surface roughness of Ra=1.5 μmfollowed by metallizing using commercial silver spraying.

A series of coated samples was produced using the modified Watts bathwith the addition of TiO₂ particles (particle size <1 μm) ranging from50 g/l to 500 g/l. Table 8 illustrates the properties of the deposits.

TABLE 7 Electroplating Conditions Deposition Temperature [° C.] 60 DutyCycle [%] 25 Deposition Rate [μm/hr] 40 Average Coating Thickness: [μm]120 Average Grain Size: [μm] 0.015 Ratio Coating Thickness/Grain Size8,000

TABLE 8 Co—TiO₂ Metal Matrix Composite Properties Grain- Bath TiO₂Dispersant Size Con- Con- of Co TiO₂ Fraction Micro- centrationcentration deposit in Deposit hardness Sample [g/l] [g/l] [nm] [Volume%] [VHN] Control 0 0 16 0 490 1 50 0 15 19 507 2 100 1.5 15 23 521 3 2003 17 32 531 4 300 6 17 38 534 5 500 12 16 37 541

Example 8 n-NiP Faceplates/Brush Plated HT Prepare Laminate GluingTogether with Adhesive

10×10 cm wide, 50 μm thick nanocrystalline Ni-0.6P foils (average grainsize: 13 nm, 780 VHN) were deposited onto a polished Ti cathode immersedin a modified Watts bath for nickel as described in U.S. Ser. No.10/516,300 (=WO2004/001100). A soluble anode of Ni rounds contained in atitanium wire basket was used. The following plating conditions wereemployed:

Average current density: 150 mA/cm²

Duty Cycle: 100%

Deposition Rate: 0.075 mm/hrElectrolyte temperature: 65° C.Electrolyte circulation rate: 0.15 liter per min and cm² cathode area

The electrolyte used comprised 137 g/l nickel sulfate, 36 g/l nickelcarbonate, 4 g/l phosphorous acid and 2 g/l saccharin. Theelectroplating conditions and metallic layer properties used aresummarized in Table 9. The fine-grained Ni-0.6P foils were subsequentlyheat-treated as indicated to further enhance the mechanical propertiesby precipitation hardening.

A laminate part was prepared by stacking and joining 10 heat-treatedNi-0.6P foil samples heat-treated at 400° C. using an epoxy resinadhesive (3M™ Scotch-Weld™ Epoxy Adhesive 1838 B/A; www.3m.com). FIG. 3shows a cross-sectional view of the laminate. The laminate was cut tosize for use as a face plate insert on a golf club head.

TABLE 9 Electroplating Conditions Deposition Temperature [° C.] 65 DutyCycle [%] 100 Deposition Rate [μm/hr] 50 Average Coating Thickness: [μm]50 Average Grain Size: [μm] 0.013 Ratio Coating Thickness/Grain Size3,846 Hardness [VHN] 780 Hardness after Heat Treatment 890 (400° C./20min) [VHN] Hardness after Heat Treatment 1010 (400° C./20 min + 200°C./11 hrs) [VHN]

Alternatively, fine-grained metal and metal-alloy foils can be preparedby CVD or PVD; e.g., using a reel-to-reel system. Similarly, coldspraying as described in U.S. Pat. No. 5,302,414 can be used to e.g.prepare fine-grained metal and metal-alloy layers.

Example 9 n-NiFe Tape on Graphite/Epoxy Resin Mountain Bike Frame Tube

Using a drumplater nanocrystalline Ni-25Fe alloy foils (average grainsize 15 nm, Hardness: 750Vickers) were deposited on a rotating Ti drumpartially immersed in a modified Watts bath for nickel as described inU.S. Ser. No. 10/516,300 (=WO2004/001100) and in Example 8. The 15 cmwide 100 μm thick nanocrystalline foil, was electroformed onto the drumcathodically, using a soluble anode made of a titanium wire basketfilled with Ni rounds using a current density of 150 mA/cm² and 100%duty cycle at 60° C. The electrolyte circulation rate remained at 0.15liter/min/cm² cathode area. The electrolyte contained 260 g/lNiSO₄.7H₂O, 45 g/l NiCl₂.6H₂O, 12 g/l FeCl₂.4H₂O, 45 g/l H₃BO₃, 46 g/lSodium Citrate, 2 g/l Saccharin, 2.2 ml/l NPA-91 at pH 2.5. The ironconcentration in the bath was maintained by continuous addition of anIron solution containing 81 g/l FeSO₄.7H₂O, 11 g/l FeCl₂.4H₂O, 13 g/lH₃BO₃, 9 g/l Sodium Citrate, 4 g/L H₂SO₄ and 0.5 g/l Saccharin at pH 2.2at an addition rate of addition: 0.3 l/hr.

A self adhesive fine-grained metal tape was prepared by applying acommercial pressure sensitive adhesive (Dow Corning® PSA-7355;www.dowcorning.com) on one side, followed by curing and slitting theadhesive tape into 1″ wide strips. The tape was spirally wound onto theouter periphery of a graphite/epoxy resin mountain bike frame after itwas mechanically abraded using Scotch-Brite® to a surface roughness ofRa=0.75 μm to permanently bond it thereto as illustrated in FIG. 4 toprovide improved stiffness, surface hardness and impact resistance.

Example 10 Grille Guard or Something Automotive

A blow-molded 6 mm thick PC/ABS truck grille-guard as illustrated inFIG. 5 did not meet the deflection and vibration requirements for thisautomotive application namely a deflection of less than 1″ with a 2501bforce applied and a first natural frequency of above 30 Hz. Uponanalysis, stiffening by increasing the plastic thickness required tostiffen the part went beyond the limitations of the blow molding processused. To meet the stiffness requirements, formed steel brackets screwedonto the back plate could be used but increases the cost and weight ofthe grille guard. A 0.001″ (0.025 μm) thick lightweight, fine-grainedNi-20Fe coating was applied to reinforce the part after abrading thesurface to be coated to an average surface roughness of Ra=0.6 μm. Theaddition of the fine-grained metal layer to the polymer partsubstantially increased the stiffness of the part and met the deflectionand frequency performance required. The fine-grained Ni-20Fe coatingonly added 153 grams of weight to the part, keeping it below the targetweight of 50 lbs. FIG. 6 shows the deflection of grille guard containinga fine-grained metallic coating with 250 lbf applied at the cross beam.The maximum deflection tolerated is 1″ (25 mm) and the deflectionencountered with the part as illustrated is 24.6 mm. Similarly, withrespect to the natural frequency the grille guard containing afine-grained metallic coating displayed a frequency of 30.3 Hz which metthe requirement of the target frequency of over 30 Hz.

As illustrated in Table 10, although other metallic coatings would addthe same stiffness due to similar Young's modulus, they would have notbeen able to withstand the high stresses (250 MPa at 10° C. resulting in1,500 MPa over full temperature range) placed on the coating. Highstresses would also be encountered when applying the 250 lbf load whenup to 900 MPa of stress would be placed on the coating. Table 11summarizes the various design iterations; only the design with then-Ni-20Fe coating met all of the performance criteria.

TABLE 10 Yield Strength Comparison of Selected Metallic MaterialsMetallic Coatings Elastic Modulus [GPa] Yield Strength [MPa]Conventional Ni 185 220 Sulfamate Ni 185 <550 Nicoloy 185 <1000Fine-grained Ni—20Fe 185 1785

TABLE 11 Summary of Performance Results 1^(st) Natural Static Def.Frequency Plastic (specification: (specification: Part Thickness <25mm) >30 Hz) Part Mass PC/ABS 4 mm >100 mm    16 Hz 5.2 kg PC/ABS + 6 mm36 mm 30 Hz 9.5 kg Steel brackets Stiffer PC/ABS 6 mm 33 mm 26 Hz 7.8 kgStiffer PC/ABS 6 mm 24.6 mm   30.3 Hz   8.0 kg with 0.001″ n-Ni—20Fecoating

Example 11 n-NiFe Coated ABS Running Board

To demonstrate the benefits of polymer parts reinforced with ananostructured material, commercial stainless steel automotive runningboards were sourced. Standard 3.5″ OD PC/ABS tubes were also obtainedfor plating to achieve a structural shell with similar stiffness to thesteel running board. After suitable activation (initially, the substratesurface was roughened with Scotch-Brite® to enhance coating adhesion);each tube was metallized using silver spray, followed by a Cu pre-plateto render it conductive enough for subsequent electrodeposition of thefine-grained material. The entire outer surface was coated with a layerof n-Ni-20Fe (average grain size 20 nm) as described in Example 5 to athickness of 0.009″. The average surface roughness was varied betweenRa=0.5 μm and Ra=15.0 μm by changing the abrasive media accordingly.After the application of the fine-grained coating, the surface roughnessdecreased to between about ½ and ⅔ of the original value due to theleveling effect of the electrodeposited layer. Sections of the originalmetal running board and nanocoated PC/ABS running boards are shown inFIG. 7.

Table 12 indicates that a 3.5″ diameter PC/ABS tube with a 0.009″coating of n-Ni-20Fe (average grain size 20 nm) enhances the stiffnessof the polymer part to be equivalent to the steel part yet yield a 43%weight savings.

TABLE 12 Results of Stiffness Analysis for Nanoplated Running Boards 304PC/ABS Stainless 30% glass PC/ABS Substrate Steel fill 30% Glass FillOutside Diameter [in] 3.0 3.5 3.5 Thickness [in] 0.06 0.71 0.13 Density[g/ml] 8 1.31 1.31 E-Modulus of Elasticity [MPa] 205 8 8 EI-Stiffness [N· m²] 52.0 21.4 6.3 Length [cm] 200 200 200 Mass [kg] 5.82 10.49 2.26Fine Grained Coating N/A N/A n-Ni—20Fe Thickness [in] — — 0.009 Density[g/ml] — — 8.6 E-Modulus of Elasticity [MPa] — — 185 EI-Stiffness [N ·m²] — — 45.7 Mass [kg] — — 1.07 Finished Product 304 PC/ABS PC/ABSStainless 30% glass 30% Glass Fill- Steel fill n-Ni—20Fe EI-Stiffness [N· m²] 52.0 21.4 52.0 Mass [kg] 5.82 10.49 3.33 Weight Savings 0 −80 43versus 304 SS [%]

The nanostructured coatings passed standard peel tests, although it wasobserved that the coating adhesion improved significantly withincreasing the surface roughness of the substrate before plating.Specifically a surface roughness of the substrate in the Ra=0.25 μm toRa=5.0 μm range proved particularly beneficial while not compromisingthe appearance. Selected parts were exposed to a variety of mechanicaltests. The results indicated that hybrid nanostructured metal/polymerrunning boards provided adequate durability and performance whilereducing the weight by 40-50% when compared with, e.g., steel runningboards.

Similar performance benefits are achieved when substrates includingcarbon/epoxy, PTOs, polyamide, polypropylene and wood were coated usingthe same approach.

VARIATIONS

The foregoing description of the invention has been presented describingcertain operable and preferred embodiments. It is not intended that theinvention should be so limited since variations and modificationsthereof will be obvious to those skilled in the art, all of which arewithin the spirit and scope of the invention.

1. An article comprising: i) a permanent substrate comprising apolymeric material; and ii) a fine-grained metallic material having anaverage grain size between 2 nm and 5,000 nm, a thickness between 25 μmand 5 cm, a hardness between 200 VHN and 3,000 VHN, said fine-grainedmetallic material covering at least a portion of said permanentsubstrate. 2-34. (canceled)
 35. An article according to claim 1 whereinsaid portion has a surface roughness in the range of Ra=0.25 μm to Ra=25μm.
 36. An article according to claim 1, wherein said metallic materialis selected from the group consisting of: i) a pure metal selected fromthe group consisting of Ag, Al, Au, Cu, Co, Cr, Ni, Sn, Fe, Pt, Ti, W,Zn and Zr, ii) an alloy containing at least two elements selected fromthe group consisting of Ag, Al, Au, Cu, Co, Cr, Ni, Sn, Fe, Pt, Ti, W,Zn and Zr; iii) pure metals selected from the group consisting of Ag,Al, Au, Cu, Co, Cr, Ni, Sn, Fe, Pt, Ti, W, Zn and Zr and alloyscontaining at least two of these, further containing at least oneelement selected from B, C, Mo, Mn, P, S, Si, Pb, Pd, Rh, Ru, Sn and V;iv) any of (i), (ii) or (iii) where said metallic coating also containsparticulate addition in a volume fraction between 0 and 95% by volume.37. An article according to claim 36, wherein said particulate additionis one or more materials selected from the group consisting of metals,metal oxides, carbides, carbon, ceramics, glass and polymer materials.38. An article according to claim 1, wherein said permanent substrate isa filled or unfilled polymeric material selected from the groupconsisting of epoxy resin composites, polyamide, glass filled polyamide,polyester, polythalamide, polypropylene, polycarbonate, polyvinylchloride (PVC), thermoplastic polyolefins (TPOs), polycarbonate andacrylonitrile-butadiene-styrene (ABS).
 39. An article according to claim38, wherein said filled polymeric material contains a filler selectedfrom the group consisting of glass, glass fibers, carbon, carbonnanotubes, graphite, graphite fibers, metals, metal alloys, ceramics andmineral fillers.
 40. An article according to claim 1, wherein saidfine-grained metallic material has a yield strength of at least 300 MPa.41. An article according to claim 1, containing an intermediateconductive layer between said metallic material and said permanentsubstrate.
 42. An article according to claim 41, where the intermediateconductive layer comprises a metallic layer constituted of Ag, Ni or Cuor a combination of any two or all of these.
 43. An article according toclaim 41, where the intermediate conductive layer comprises polymericmaterial with conductive particulates therein.
 44. An article accordingto claim 43, where the conductive particulates are composed of orcontain Ag, Ni or Cu or graphite or other conductive carbon or acombination of two or more thereof.
 45. An article according to claim41, where the intermediate conductive layer is a conductive paint or aconductive epoxy.
 46. An article according to claim 1, containing apolymeric adhesive material between the permanent substrate and thefine-grained metallic material.
 47. An article according to claim 1,wherein said article is a component or part of an automotiveapplication.
 48. An article according to claim 47, where the componentor part is selected from the group consisting of brackets, fuel rails,spoilers, muffler tips, wheels, vehicle frames, grill guards, pedals,brake pedals and running boards.
 49. An article according to claim 47 or48, wherein the fine-grained metallic material is constituted of atleast one metal selected from the group consisting of Ni, Co and Fe. 50.An article according to claim 1, which has a tubular structure and saidfine-grained metallic material extends over at least part of an inner orouter surface of said tubular structure.
 51. An article according toclaim 50, wherein said permanent substrate comprises a polymericmaterial containing filler selected from the group consisting of glass,glass fibers, graphite, graphite fibers, carbon, carbon fibers andcarbon nanotubes.
 52. An article according to claim 50, wherein thefine-grained metallic material has a hardness of greater than 200 VHNand a ratio of thickness to grain size of greater than 1,000.
 53. Anarticle according to claim 1 having a fine-grained metallic materialcoating on a substrate, wherein the weight of the fine-grained metallicmaterial is between 5% and 95% of the total weight of the article. 54.An article according to claim 53, wherein said fine-grained metallicmaterial is constituted of a Ni, Co or Fe based alloy.
 55. An articleaccording to claim 53, which is an automotive part.
 56. An articlecomprising a fine-grained metal material coated polymeric materialcomposite having a yield strength of at least 25 MPa wherein: i) theweight of the fine-grained metallic material coating is between 5% and95% of the total weight of the article; ii) said article having atorsional or bending stiffness per unit weight improved by at leastabout 5% when compared to the torque or moment of the same article notcontaining the metallic material coating.
 57. An article according toclaim 56, wherein said fine-grained metallic material coating is presenton at least part of an inner or outer surface of the composite.
 58. Anarticle according to claim 57, wherein said article is a component orpart of an automotive application.
 59. An article according to claim 58,where the component or part is selected from the group consisting ofbrackets, fuel rails, spoilers, muffler tips, wheels, vehicle frames,grill guards, pedals, brake pedals and running boards.
 60. An articleaccording to claim 56, which has a tubular structure and saidfine-grained metallic material extends over at least part of an inner orouter surface of said tubular structure.
 61. An article comprising apolymeric material, having a surface at least partially coated with afine-grained metallic material having a grain size of between 2 nm and5,000 nm and a yield strength of at least 300 MPa.
 62. An articleaccording to claim 61, wherein said surface which is at least partiallycoated has a surface roughness in the range of Ra=0.25 μm to Ra=25 μm.63. An article according to claim 61, wherein said coating is on anoutside surface of said polymeric material and has a thickness rangingfrom about 25 μm and 5 cm.
 64. An article according to claim 61, whereinsaid polymeric material is reinforced.
 65. An article according to claim61, containing a metallized layer between said polymeric material andsaid fine-grained metallic coating.
 66. An article according to claim61, wherein said article is a component or part of an automotiveapplication.
 67. An article according to claim 66, wherein saidcomponent or part is selected from the group consisting of brackets,fuel rails, spoilers, muffler tips, wheels, vehicle frames, grillguards, pedals, brake pedals and running boards.
 68. An articleaccording to claim 61, which has tubular structure and said fine-grainedmetallic material extends over at least part of an inner or outersurface of said tubular structure.
 69. An article comprising i) apolymer substrate, and ii) a fine grained metallic layer having a grainsize in the range of 2 nm to 5,000 nm, a thickness ranging from 25 μm to5 cm, a modulus of resilience ranging from 0.25 MPa to 25 MPa and saidfine grained layer covering at least a portion of said polymer substrateand the weight of said fine grained metallic layer ranging from 5% to95% of the weight of said article.
 70. An article according to claim 69,wherein its torsional or bending stiffness per unit weight is improvedby at least 5% when compared to the torque or moment of an article thesame but not containing (ii).
 71. An article according to claim 69,wherein said portion of said polymer substrate has an average surfaceroughness of Ra 0.25 μm to 25 μm.
 72. An article according to claim 71,wherein said article contains a layer intermediate (i) and (ii) selectedfrom the group of a metallic intermediate layer, a polymeric adhesiveintermediate layer and a conductive polymeric intermediate layercontaining conductive particulates.
 73. An article according to claim72, wherein said article is a component or part of an automotiveapplication.
 74. An article according to claim 73, wherein saidcomponent or part is selected from the group consisting of brackets,fuel rails, spoilers, muffler tips, wheels, vehicle frames, grillguards, pedals, brake pedals and running boards.
 75. An articleaccording to claim 69, which has a tubular structure and saidfine-grained metallic material extends over at least part of an inner orouter surface of said tubular structure.